Dichlorobenzaldehyde-oxime-carbonates

ABSTRACT

Dichlorobenzaldehyde-oxime-carbonates are prepared, and used per se or as active ingredients in herbicide compositions.

United States Patent Puttner et al. June 17, 1975 01C HLOROBENZALDEHYDE-OXIME- CARBONATES [56] References Cited [75] Inventors: Reinhold Puttner; Friedrich Arndt, UNITED STATES PATENTS both of erl G y 3,165,392 1/1965 Koopman 260/566 AE 3,644,524 2/1972 Cahoy 260/566 AB [73] Schema Berhn Germany 3,732,306 5/1973 Cutman CI al 260/566 AB [22] Filed: June 28, 1973 Primary Examiner-Gerald A. Schwartz [21] Appl' 374496 Attorney, Agent, or Firm-Joseph F. Padlon [30] Foreign Application Priority Data 7 ABSTRACT July 13, Germany Dichlor0benzaldehyde oxime carbonates are p 52] 0.5. CI 260/566 AE; 71/121 8121 Se as acme ngred'ems [51] Int. Cl. C07c 131/00 [58] Field of Search 260/566 AB 5 Claims, N0 Drawings DICHLOROBENZALDEHYDE-OXIME- CARBONATES The invention refers to new 2,6-

dichlorobenzaldehyde-oximecarbonates, methods for their production, and to herbicides containing these compounds as active ingredients.

Until now, few compounds have become known which are suitable for the inhibiting or controlling the growth of plants for the purpose of combating undesirable plant growth. Among these so-called inhibitors it should be noted 2,o-dichlorobenzonitrile, US. Pat. No. 3,027,248, which, however, does not always satisfy the requirements for the practice of effectively inhibiting or controlling plant growth.

Another growth inhibitor known in the art is maleic acid hydrazide (l,2-dihydropyridazine-3-6-dione), an active substance which is known to inhibit especially grasses in their growth, of German Patent No. 815,192. As a disadvantage in the use of this compound, it has been found, however, that in the comparatively low quantities applied, the effect is insufficient.

It is, therefore, essentially an object of the present invention to develop a more effective agent in comparison with the known inhibitors.

It has now been found that compounds of the general formula:

in which R, and R are identical or different, and represent, respectively, a monoor multi-substituted aromatic, aliphatic, cycloaliphatic or araliphatic hydrocarbon radical or in which R, and R together with the carbon atom represent a monoor multisubstituted cycloaliphatic hydrocarbon radical, are herbicidal and show a better effect on undesired plant growth than presently known agents.

In this connection there enter into consideration for R and R as aromatic hydrocarbon radicals such as the phenyl or the naphthyl radical; as'aliphatic hydrocarbon radicals, such as those with l to 12 carbon atoms; namely, methyl, ethyl, propyl, isopropyl, butyl and others; as cycloaliphatic hydrocarbon radicals those with 5 to 8 carbon atoms, such as cyclohexyl and others, and as araliphatic hydrocarbon radicals, as benzyl or phenylethyl and others, these radicals being, for example, identically or differently substituted by the low alkyl radicals, such as, methyl or ethyl; halogen atoms, such as chlorine or bromine; low alkoxy radicals; such as methoxy or ethoxy and others.

R and R in the formula may also form a cycloaliphatic 5- to 8-membered ring; for example, cyclohexyl or cyclooctyl and others, which may be monoor multisubstituted by the low alkyl radicals, as methyl, etc.

The compounds according to the invention show above all a strong, inhibiting effect on growing meristematic tissue, such as the vegetation points and root tips. They also prevent germination and growth of seedlings and thus combat growth of monoand dicotyledonous plant species. Such species are Stellaria media, Senecio vulgaris, Matricaria chamomilla, Lamium amplexicaule, Cenzaurea cyanus, Amaranthus retroflexus, Galium aparine, Chrysanthemum segetum, Avena fatua, Alopecurus myosuroides, Echinochloa crus galli, Setaria italica, Agropyron repens, Cynodon dactylon, Cyperus esculentus, Cyperus rotundus, Sorghum halepense, Ipomea purpurea, Polygonum lapathifolium, Digitaria sanguinalis, Lolium perenne, Setaria faberii, Rumex crispus, Taraxacum officinale and Artemisia vulgaris.

It has also been found that by using the compounds according to the invention the growth of the sprout of persistent weeds is suppressed if the treatment occurs before or at budding. In this way, for example, it is possible to combat Agropyron repens, Artemisia vulgaris, Rumex crispus, Taraxacum officinale, Cynodon dactylon, Sorghum halepense, Cyperus esculentus, Cyperus rotundus, Pteridium aquilinum and Equisetum ssp. This effectiveness signifies a substantial technical improvement particularly since if the compound is not used the named weeds have proliferated to such an extent in some areas they make the profitable utilization of the tilled field questionable.

Another major advantage in the use of the compounds according to the invention is their particular compatibility with crop plants, which are not impaired by the treatment. For example, weeds in orchards, berries, ornamental trees, plants and shrubs and in planted rice can be combated without damage to their cultivation.

For the described purposes there are suitable among the compounds according to the invention particularly those where in the defined general formula the radicals R and R are identical and represent an alkyl radical with 1 to 3 carbon atoms, such as methyl, ethyl or propyl, or the phenyl radical.

The quantities used in application are, depending on area of use and type of plant, between about 1 and 5 kg active substance per hectare. For total weed control and also for the control of aquatic plants, higher quantities to about 10 kg of active substance per hectare or in special cases even more can advantageously be used.

The compounds according to the invention can be used either alone or in mixtures with one another, and also in mixtures with other plant protection and pest control agents. If an additional widening of the spectrum of action is intended, other herbicides also may, for example be added, whereby synergistic effects may be expected.

Depending on the purpose of use, other substances also may be added. Such substances are non-phytotoxic additions which may result in producing synergistic effects with herbicides. They are wetting agents, emulsifiers, solvents, oily additions and others.

Advantageously, the active substances according to invention or their mixtures are used in preparations, such as powders, scatters, granulations, solutions, emulsions or suspensions, with the addition of liquid and/or solid vehicles or diluents and possibly wetting adhesive, emulsifying and/or dispersing aids.

suitable liquid vehicles such as water, aliphatic and aromatic hydrocarbons, like benzene, toluene, cyclohexanone, isophorone, as mineral oil fractions may be used.

Suitable solid vehicles that may be used are mineral earths such as siliceous clay, silica gel, talc, kaolin, attaclay, limestone, silica and plant products, such as flours.

Among the surface-active substances that may be used are: calcium lignin sulfonate, polyoxyethyleneoctylphenol ether, naphthalene sulfonic acids, phenol sulfonic acids, formaldehyde condensates, fatty alcohol sulfates and fatty acid alkali and alkaline earth salts.

The proportion of the active substance or substances in the various preparations mayvary within wide limits. For example, the'agents contain about 20 to 80 percent by weight of active substances, about 80 to 20 percent by weight of liquid or solid vehicles and possibly up to 20 percent by weight of surface-active substances.

The agents can be applied in the usual manner. For example, with water as the vehicle in spray solution, quantities of 100 to 1000 liters per hectare may be used. For total weed control, also the partly common quantities of more than 1000 liter/ha may be readily applied. Also, the use of the agents in the socalled Ultra-low-v'olume process is possible. 'Likewise', the agents may be used in microgranulate form.

The use is also carried out by spraying or scattering the agents ready for use on the still weed-free ground. By working the agents into the ground, their effectiveness is, as a rule; increased.

The-identified new compounds are produced for example, by reacting 2,6-dichloro-benzaldehyde oxime of the formula 1 -cu N on or the alkali salt thereof, 'such as the sodium or potassium salt, with a compound of the general formula (III) l.' lsopropylidenamino-(2,6-dichlorobenzylidenamino)-carbonate To" a solution of 19 g (0.1 mole) 2,6-

dichlorobenzaldehyde oxime and 10.1 g (0.1 mole) triethylamine in 200 ml chloroform a solution of 13.55 g (0.1 mole) 2-oximino-proparie-O-carboxylic acid chloride in 50 ml of chloroform is added drop by drop with intense agitation at -lO to -5 C; After this, the reactionmixture is left standing for one hour at 0 C. The reaction mixture is then poured into iced water and the organic phase washed with iced water three times. The product is dried with magnesium sulfate and evaporated under reduced pressure. The residue is treated with methanolf Yield: 20.2 g 70% of the theory l a. This compound can also be produced as follows:

To 1 a suspension of 4.24 g (0.02 mole) 2,6- dichlorobenzaldehyde-oxime sodium in l00 ml methylene chloride there is added while stirring intensively at 1 5, a solution. of 2.71 g (0.02 mole) 2-oximinopropane-0-carboxylic acid chloride in 50 ml methylene chloride drop by drop. This is stirred for 31hours at -5 to 0 C. The reaction mixture is filtered and the methylene chloride removed under vacuum. The colorless residue is recrystallized from methanol.

Yield: 3.7 g 64% of the theory 2. Diphenylmethylenamino-(2,6-dichlorobenzylidenamino)-carbonate To a suspension of 19 g (0.1 mole) 2,6- dichlorobenzaldehyde-oxime in 200 ml chloroform there are added simultaneously drop by'drop while stir-.

ring intensively at l 5 C to l0 C a solution of 25.97 g (0.1 mole) benzophenone-oxime-O-carboxylic acid chloride in ml chloroform and a solution of 10.1 g

(0.1 mole) triethylamine in 50 ml chloroform. Thereafter the reaction mixture is left standing for one hour at 0 C. The reaction mixture is poured into iced water and the organic phase washed three times with iced water. The product is dried with magnesium sulfate and evaporated under reduced pressure. The residue is then treated with methanol.

Yield: 28.2 g'= 68% of the theory M.P. 92 101C By this process, it is also possible to produce for example l-phenylethylidene-amino-(2,6- dichlorobenzylidene-amino)-carbonate of the M.P. l07-l 10 C. t

The compounds according to invention are practically colorless and odorless, usually crystalline substances. They are insoluble in water and gasoline and slightly soluble in acetone, tetrahydrofurane, cyclohexanone, isophorone and dimethyl formamide.

The starting products for the production of the compounds according to the invention are known or can be produced by known methods.

The production of the preparations of the compounds according to the invention and of their mixtures, ready-for use, can be carried out in a known manner, suchas by mixing or grinding. If desired, the individual components may be mixed only just before their use, as is done in'the practice for example, in the socalled tank mix process.

The following examples will show the herbicidal effect of the compounds according to invention.

EXAMPLE 1 The compounds listed in the table were sprayed on virgin soil in the greenhouse at a dose of 3 kg active substance per hectare and then worked into the soil. The compounds were present as aqueous suspensions, which were applied at 500 liters per hectare. Then the plants listed in the following table were sown. I

The rating was effected 3 weeks after the treatment by'determining the degree of damage of the plants, using the rating code 0 -l0 with 0 totally destroyed or inhibited and l0-= not damaged.

The findings show the superior effect of the agents to be used according to the invention.

-C()l1til'ltld A Diphenlymeth lenuamino-t2.ti-diehlorohemylideneumino)-e:|rhomne B -'-'lsopropylidencuminwtlo-dichlorohenyylitleneaminui-earhonate l-phenylethylidcneaminu-t2.fi-dlchl trobenzylideneuminnt-carhonnte Compounds (om- Unl) Maleic acid hydrmitte according parison treated a -=totall dcstroyedorinhibited to invention agent Control 10 not damaged Cucumber 0 (l l0 Alfalfa o o 0 2 t0 EXAMPLE 2 Spinach 0 0 0 5 Bush bean t) 0 l 10 21:30a 8 The compounds listed in the following table were s fl U 0 Q l m 10 sprayed in the greenhouse in a dose of 3 kg active subgg i 8 g stance per hectare before the sprouting of the plants. Wheat 0 0 0 m The agents were applied as an aqueous suspension in garley l2 I8 500 liters per hectare. The rating was effected 4 weeks 0 0 0 5 after the treatment by determining the degree of dam- Rice 0 o (1 5 10 age of the plants, using the rating code 0-10 with 0 Marrow-stem kale 0 0 (l l l0 I M wimflrupc 0 0 0 m totally destroyed or inhibited and 10 not dam- Pea o o 0 l 10 g 9 f 0 0 0 3 10 The test values show the better inhibition of the .Su-Ilur: media 0 0 0 l0 l() f h h .s'i-m-t-m t'ulgurix o 0 o x 10 2O sproutlng L P ante W the dgems according Mutrit'uriu r'lmmumillu 0 0 0 5 10 to th@ ll'lVClltlOn.

Compound according to invention A B C D E F G H l .l

lsopropylideneamino-( 2,6- tlichlorohenzylideneamino )warhonate l 0 0 0 0 0 0 0 0 0 Comparison agent 2 6-dichlorobenzonitrile 0.5 0 l 0 2 3 0 0 0 3 Untreated l0 l0 l0 l0 l0 l0 l0 l0 l0 It) A Rumux (fix nix B 'l'uraxucum qtficinale C =uru'mis'iu vulgurix D Dam-x carom E Vida ("mu-u F Rulmscatnriux G Puu [)fllll'HXiA' H Ft'Slllt'tl Rulmi l Brunms ssp, J Agmpymn repent 0 Totally destroyed or inhibited I0 not damaged Lamium umploxit'uule (l 0 0 1 l0 EXAMPLE 3 ('t'ntaurr'a cyunux 0 0 (l 2 l0 21:22:22gxzial 3 40 In a test experiment, dry filter paper was sprayed with I ('hrysumlwmum .vegt'lum 0 0 0 2 it) compounds named below m quantltles Correspondjnufu1lm 1 mg to a rate of 0.04, 0.02, 0.01 and 0.005 kg of active UPC'K'UTUX myuxurrm (S l I 1 Edmmhmu (Wu/['- 0 0 0 3 l0 substance per hectare 1n the form of an aqueous sus- Seluriu imlica o 0 o 3 10 pension at 500 liters per hectare.

Q 45 One, three and six days, respectively, after the treat- Inlygunum lupathiufiilium 0 o 0 3 10 ment, seeds of meadow grass per test section were Qte m sungqflilwli-t 0 0 0 3 l0 placed on the paper and caused to germinate by wet- -Swarm faht'ru 0 0 0 8 l0 tmg w1th water.

Compound according to invention B C D E F G H l .l K

lsopropylideneamino- (2,6dichlorohen1.ylideneamlno-carbonatc l0 l0 l0 l0 l0 l0 l0 l0 l0 l0 10 Comparison agent A B C D E F G H l J K Zb-dichlorohenzonitrile 6* 3* 5 4 5 4 l0 5 0 3 5 Untreated l0 l0 l0 l0 l0 l0 l0 l0 l0 l0 10 A Apple seedling B 2-year vine C cauliflower D Alfalfa lei Bush hean F Cotton (l Peanut H Sunflower 1 Potato .l Manon-stem kale K Pea 0 Totally destroyed or inhibited 0 not damaged Shout damage we Claimi togeather R, and R form a cycloalkyl radical hav- 1. Compounds of the general formula: i g f o 5 to 8 carbon atoms.

2. Compounds according to claim 1, where R and R Cl are identical and represent an alkyl radical with l to 3 l carbon atoms or a phenyl radical. -CH=N O- O-N C R 3. A compound of the formula set forth in claim 1 Cl 2 which is lsopropylideneamino-(2,6-dichlorobenvlideneamino)-carbonatc. l0 4. A compound of the formula set forth in claim 1 wherein R, and R are individually selected from the which is Diphenylmethylcneamino (zq6 dichlomben group consisting of an alkyl radical having from I zylideneaminoyearbonam to 12 Carbon atoms a cycloulkyl radical f 5. A compound of the formula set forth in claim 1 from to 8 carbon atoms, a lower alkoxy radical, which is 1 (phenylethylidencamino (2,6

a phenyl radical a naphthy] radical a benzyl radi l5 dichlorobenzylidene-amino)-carbonate. cal. 21 phenylethyl radical, and when taken is 

1. COMPOUNDS OF THE GENERAL FORMULA:
 2. Compounds according to claim 1, where R1 and R2 are identical and represent an alkyl radical with 1 to 3 carbon atoms or a phenyl radical.
 3. A compound of the formula set forth in claim 1 which is Isopropylideneamino-(2,6-dichlorobenzylideneamino)-carbonate.
 4. A compound of the formula set forth in claim 1 which is Diphenylmethyleneamino-(2,6-dichlorobenzylideneamino)-carbonate.
 5. A compound of the formula set forth in claim 1 which is 1-(Phenylethylideneamino-(2,6-dichlorobenzylidene-amino)-carbonate. 